Defluorinating agent for gas-phase fluorine-containing hydrogen chloride and preparation method of defluorinating agent

Abstract

The invention relates to a defluorinating agent for gas-phase fluorine-containing hydrogen chloride and a preparation method of the defluorinating agent. The invention firstly relates to a defluorinating agent which comprises the following raw materials: a) an active ingredient which is a metal compound MX, M is metal, and X is an atom or an atomic group or an ion which forms a compound with M; the invention relates to a defluorinating agent, which comprises a) a carrier, c) a strength agent, d) a binder, e) an extrusion aid and f) a peptizing agent, and is prepared by a method comprising the following steps: 1) mixing components a) to f) to obtain a first mixture; 2) forming the first mixture to obtain first particles; and (3) the first particles are treated at the temperature T1, the defluorinating agent is obtained, and the temperature T1 ranges from 500 DEG C to 700 DEG C.

Description

Technical Field

[0001] The invention relates to the technical field of adsorbents, in particular to an efficient defluorinating agent and a preparation method thereof. The defluorinating agent is suitable for removing hydrogen fluoride in a gas phase or a liquid phase, and in particular exhibits excellent defluorinating performance in the treatment of fluorine-containing hydrogen chloride gas. Background Art

[0002] The fluorine chemical industry has emerged since the 1930s. Due to its excellent product performance, wide variety and wide application fields, it has become a rapidly developing important industry. Chlorine is one of the important raw materials, and there is a large demand for the production of trichloroethane, trichloroethylene and other intermediate materials for polytetrafluoroethylene and polyvinylidene fluoride. However, chlorine usually produces hydrogen chloride or hydrochloric acid after reaction, and is mixed with hydrogen fluoride, which adds obstacles to the downstream application and recycling of the by-product hydrogen chloride / hydrochloric acid. Therefore, the effective removal of hydrogen fluoride in hydrogen chloride gas or hydrochloric acid is a key issue that needs to be solved in the healthy development of the fluorine chemical industry.

[0003] At present, the defluorination technologies for fluorine-containing hydrogen chloride gas include wet defluorination and dry defluorination. Wet defluorination includes chemical precipitation defluorination and steam stripping defluorination. Chemical precipitation defluorination removes fluoride ions by adding specific chemical substances to form a precipitate, such as the calcium chloride solution + boric acid / potassium chloride mixed solution series developed by Lanzhou University Huai'an High-tech Research Institute (CN106744688A) and the triethylamine solution defluorination developed by Duofuduo (CN111777514A); steam stripping defluorination increases the contact between gas and liquid by introducing gas, promoting the transfer of fluoride from liquid phase to gas phase, such as the steam stripping defluorination reaction system developed by Jiangsu Sanmei Chemical (CN111847382A) and the distillation separation and purification system developed by Hangzhou Juwei Technology (CN113860256A).

[0004] Dry defluorination is a method of removing fluorine-containing waste gas by passing it through an adsorption device filled with solid adsorbents, so that hydrogen fluoride reacts with the adsorbent and then is removed. It is also called chemical adsorption. The range of adsorbents is relatively wide, and various alkali metal fluorides, oxides, hydroxides, carbonates, chlorides, sulfides and other metal inorganic compounds have been developed and researched, such as the alumina molecular sieve (CN103896214B) developed by Shanghai Meistech Environment, the calcium chloride / activated carbon-loaded defluorination agent (CN104128162B) developed by Zhejiang Juhua, and the alkali metal oxide adsorbent (CN106495100A) developed by Central South University.

[0005] The present application aims to provide a novel defluorinating agent and a preparation method thereof, which can effectively remove hydrogen fluoride from gaseous fluorine-containing hydrogen chloride, and has the advantages of high efficiency, low cost and easy treatment of by-products. The present application improves the adsorption and reaction capacity of the defluorinating agent to fluoride through innovative chemical formula and process flow, and provides a new solution for industrial waste gas treatment. Summary of the invention

[0006] The applicant unexpectedly found that the defluorination agent obtained by the one-pot method through the combination of specific components in the present application can efficiently remove HF from the HCl / HF mixture and has good mechanical properties (including but not limited to compressive strength) and cycle performance.

[0007] The first aspect of the present application relates to a defluorinating agent, wherein the raw materials of the defluorinating agent include:

[0008] a) an active ingredient, wherein the active ingredient is a metal compound MX, wherein M is a metal, and X is an atom or an atomic group or an ion that forms a compound with M;

[0009] b) a carrier,

[0010] c) strength agents,

[0011] d) a binder,

[0012] e) extrusion aids,

[0013] f) a peptizing agent,

[0014] The defluorinating agent is prepared by the following method comprising the following steps:

[0015] 1) mixing components a) to f) to obtain a first mixture;

[0016] 2) forming the first mixture into first particles;

[0017] 3) treating the first particles at a temperature T1 to obtain the defluorinating agent, wherein the temperature T1 ranges from 500 to 700°C.

[0018] The second aspect of the present application relates to a method for preparing a defluorinating agent, the method comprising the following steps:

[0019] 1) Mix the following components to obtain a first mixture:

[0020] a) a metal compound comprising a cation of a metal M and a counter cation X,

[0021] b) a carrier,

[0022] c) strength agents,

[0023] d) a binder,

[0024] e) extrusion aids,

[0025] f) peptizing agent;

[0026] 2) forming the first mixture into first particles;

[0027] 3) treating the first particles at a temperature T1 to obtain the defluorinating agent, wherein the temperature T1 ranges from 500 to 700°C.

[0028] The third aspect of the present application relates to the use of the defluorinating agent described in the first aspect of the present application for removing HF from a HCl / HF mixture as a raw material. DETAILED DESCRIPTION

[0029] "Scope" disclosed herein is defined in the form of lower limit and upper limit, and a given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a particular range. The scope defined in this way can be including or excluding end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a scope. For example, if a range of 60 to 120 and 80 to 110 is listed for a particular parameter, it is understood that the range of 60 to 110 and 80 to 120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3, 4 and 5 are listed, the following range can all be expected: 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4 and 2 to 5. In this application, unless otherwise specified, the numerical range "a to b" represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers. For example, the numerical range "0 to 5" means that all real numbers between "0 to 5" are listed in this document, and "0 to 5" is just an abbreviation of these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0030] In this application, unless otherwise specified, all embodiments and preferred embodiments mentioned herein can be combined with each other to form a new technical solution.

[0031] In this application, unless otherwise specified, all technical features and preferred features mentioned herein can be combined with each other to form a new technical solution.

[0032] In the present application, unless otherwise specified, all steps mentioned herein may be performed sequentially or randomly, but are preferably performed sequentially. For example, the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.

[0033] In this application, unless otherwise specified, the terms "include" and "comprising" mentioned herein may be open-ended or closed-ended. For example, the terms "include" and "comprising" may mean that other components not listed may also be included or comprised, or may only include or comprise the listed components.

[0034] In the description of this article, it should be noted that, unless otherwise specified, "above" and "below" are inclusive of the number itself, and "several" in "one or several" means two or more.

[0035] In the description herein, unless otherwise specified, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, any of the following conditions satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0036] Herein, unless otherwise specified, percentage (%) or part refers to percentage by weight or part by weight relative to the composition.

[0037] Herein, if there is no contrary description, the sum of the contents of the various components in the composition is 100%.

[0038] Herein, if there is no contrary description, the sum of the parts of each component in the composition may be 100 parts by weight.

[0039] In this document, unless otherwise specified, "a combination thereof" means a multi-component mixture of the elements described, for example a mixture of two, three, four and up to the maximum possible multi-component mixture.

[0040] If not specifically stated, the terms "a" or "an" used in the present specification means "at least one".

[0041] Herein, unless otherwise stated, all reactions are carried out at normal temperature and pressure.

[0042] The first aspect of the present application relates to a defluorinating agent, wherein the raw materials of the defluorinating agent include:

[0043] a) an active ingredient, wherein the active ingredient is a metal compound MX, wherein M is a metal, and X is an atom or an atomic group or an ion that forms a compound with M;

[0044] b) a carrier,

[0045] c) strength agents,

[0046] d) a binder,

[0047] e) extrusion aids,

[0048] f) a peptizing agent,

[0049] The defluorinating agent is prepared by the following method comprising the following steps:

[0050] 1) mixing components a) to f) to obtain a first mixture;

[0051] 2) forming the first mixture into first particles;

[0052] 3) treating the first particles at a temperature T1 to obtain the defluorinating agent, wherein the temperature T1 ranges from 500 to 700°C.

[0053] a)Active ingredients

[0054] The raw material of the defluorinating agent described in the first aspect of the present application comprises a) an active ingredient, wherein the active ingredient is a metal compound represented by the formula MX, wherein M is a metal, and X is an atom, an atomic group or an ion that can form a compound with M.

[0055] According to one embodiment, the metal M is selected from one or more of alkali metals, alkaline earth metals, Group III metals, and transition metals.

[0056] According to a preferred embodiment, the metal M is selected from one or more of Mg, Ca, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Zn.

[0057] According to a more preferred embodiment, the metal M is selected from one or more of Ca, Mg and Al.

[0058] However, those skilled in the art will appreciate that the above preferred embodiments are provided only as examples, and those skilled in the art may select other metals M as needed.

[0059] According to a preferred embodiment, X in the metal compound is selected from one or more of O, Cl, OH, and F.

[0060] According to non-limiting examples, the active ingredient may be Al(OH)3, CaCl2, MgCl2.

[0061] b) Carrier

[0062] The raw material of the defluorinating agent described in the first aspect of the present application comprises b) a carrier.

[0063] According to one embodiment, the carrier is selected from one or more of aluminosilicates, silicates, silicon dioxide, layered oxides, and carbon materials.

[0064] According to a preferred embodiment, the carrier is selected from bentonite, montmorillonite, kaolin, silica, diatomaceous earth, and porous carbon materials.

[0065] In the defluorination agent of the first aspect of the present application, the content of the carrier can be adjusted according to actual needs.

[0066] According to one embodiment, the mass of the carrier is 10% to 60%, or 15% to 60%, or 10% to 55% of the mass of the active ingredient.

[0067] According to a non-limiting embodiment, the mass of the carrier is 10%, or 10.5%, or 11%, or 11.5%, or 12%, or 12.5%, or 13%, or 13.5%, or 14%, or 14.5%, or 15%, or 15.5%, or 16%, or 16.5%, or 17%, or 17.5%, or 18%, or 18.5%, or 19%, or 19.5%, or 20%, or 20.5 %, or 21%, or 21.5%, or 22%, or 22.5%, or 23%, or 23.5%, or 24%, or 24.5%, or 25%, or 25.5%, or 26%, or 26.5%, or 27%, or 27.5%, or 28%, or 28.5%, or 29%, or 29.5%, or 30%, or 30.5%, or 31%, or 31.5%, or 32%, or 32.5%, or 33%, or 33.5%, or 34%, or 34.5%, or 35%, or 35.5%, or 36%, or 36.5%, or 37%, or 37.5%, or 38%, or 38.5%, or 39%, or 39.5%, or 40%, or 40.5%, or 41%, or 41.5%, or 42%, or 42.5%, or 43%, or 43.5%, or 44%, or 44.5%, or 45%, or 45.5%, or 46%, or 47.5%, or 48.5%, or 49.5%. 7%, or 47.5%, or 48%, or 48.5%, or 49%, or 49.5%, or 50%, or 50.5%, or 51%, or 51.5%, or 52%, or 52.5%, or 53%, or 53.5%, or 54%, or 54.5%, or 55%, or 55.5%, or 56%, or 56.5%, or 57%, or 57.5%, or 58%, or 58.5%, or 59%, or 59.5%, or 60%.

[0068] c) Strength agent

[0069] The raw materials of the defluorinating agent described in the first aspect of the present application include c) a strength agent.

[0070] According to one embodiment, the strength agent is selected from metal carbonates, metal carboxylates, metal sulfates, and any combination thereof.

[0071] According to a preferred embodiment, the metal in the strength agent is selected from one or more of calcium, magnesium, and aluminum. As non-limiting examples of the strength agent, aluminum sulfate, calcium carboxylate, calcium carbonate, and magnesium carbonate can be mentioned. However, those skilled in the art will appreciate that the above examples are provided for illustrative purposes only and are not intended to limit the present application in any way.

[0072] Those skilled in the art can adjust the amount of the strength agent according to needs.

[0073] According to one embodiment, the mass of the strength agent is 1% to 20%, or 2 to 18%, or 3 to 17% of the mass of the active ingredient.

[0074] According to a non-limiting embodiment, the mass of the strength agent is 1%, or 1.5%, or 2%, or 2.5%, or 3%, or 3.5%, or 4%, or 4.5%, or 5%, or 5.5%, or 6%, or 6.5%, or 7%, or 7.5%, or 8%, or 8.5%, or 9%, or 9.5%, or 10%, or 10.5%, or 11%, or 11.5%, or 12%, or 12.5%, or 13%, or 13.5%, or 14%, or 14.5%, or 15%, or 15.5%, or 16%, or 16.5%, or 17%, or 17.5%, or 18%, or 18.5%, or 19%, or 19.5%, or 20% of the mass of the active ingredient.

[0075] d) Binder

[0076] The raw materials of the defluorinating agent described in the first aspect of the present application include d) a binder.

[0077] According to one embodiment, the binder is selected from one or more of starch compounds, cellulose compounds, polyvinyl alcohol, sodium alginate, and chitosan.

[0078] According to a preferred embodiment, the starch compound is selected from one or more of starch, sesbania powder and guar gum.

[0079] According to a preferred embodiment, the cellulose compound is selected from one or more of methyl cellulose, ethyl cellulose, hydroxypropyl cellulose and carboxymethyl cellulose.

[0080] The amount of the binder used can be adjusted according to actual needs.

[0081] According to one embodiment, the mass of the binder is 1 to 10%, or 2 to 9% of the mass of the active ingredient. According to a non-limiting embodiment, the mass of the binder is 1%, or 1.25%, or 1.5%, or 1.75%, or 2%, or 2.25%, or 2.5%, or 2.75%, or 3%, or 3.25%, or 3.5%, or 3.75%, or 4%, or 4.25%, or 4.5%, or 4.75%, or 5%, or 5.25%, or 5.5%, or 5.75%, or 6%, or 6.25%, or 6.5%, or 6.75%, or 7%, or 7.25%, or 7.5%, or 7.75%, or 8%, or 8.25%, or 8.5%, or 8.75%, or 9%, or 9.25%, or 9.5%, or 9.75%, or 10% of the mass of the active ingredient.

[0082] e) Extrusion aid

[0083] The raw materials of the defluorinating agent described in the first aspect of the present application include an extrusion aid.

[0084] In the context of this application, the term "extrusion aid" is understood to mean a natural or synthetic compound that improves the rheological properties, lubrication properties of a material during processing or can enhance the extrusion effect of a material.

[0085] According to a preferred embodiment, the extrusion aid is selected from cellulose compounds.

[0086] According to a preferred embodiment, the cellulose compound is selected from one or more of methyl cellulose, ethyl cellulose, hydroxypropyl cellulose and carboxymethyl cellulose.

[0087] The amount of the extrusion aid can be adjusted by those skilled in the art according to the desired final properties of the defluorination agent.

[0088] According to one embodiment, the mass of the extrusion aid is 1 to 15% of the mass of the active ingredient.

[0089] According to non-limiting embodiments, the mass of the extrusion aid may be 1%, or 1.5%, or 2%, or 2.5%, or 3%, or 3.5%, or 4%, or 4.5%, or 5%, or 5.5%, or 6%, or 6.5%, or 7%, or 7.5%, or 8%, or 8.5%, or 9%, or 9.5%, or 10%, or 10.5%, or 11%, or 11.5%, or 12%, or 12.5%, or 13%, or 13.5%, or 14%, or 14.5%, or 15% of the mass of the active ingredient.

[0090] f) Peptizer

[0091] The raw materials of the defluorinating agent described in the first aspect of the present application include f) a peptizing agent.

[0092] In the context of the present application, the term "peptizing agent" is understood to mean an inorganic or organic agent which makes it possible to form a stable colloidal system.

[0093] According to one embodiment, the peptizing agent is silica sol.

[0094] The amount of the peptizing agent can be adjusted by those skilled in the art according to the desired final properties of the defluorinating agent.

[0095] According to one embodiment, the mass of the peptizing agent is 10 to 50%, or 15 to 45% of the mass of the active ingredient.

[0096] According to a non-limiting embodiment, the mass of the peptizing agent is 10%, or 11%, or 12%, or 13%, or 14%, or 15%, or 16%, or 17%, or 18%, or 19%, or 20%, or 21%, or 22%, or 23%, or 24%, or 25%, or 26%, or 27%, or 28%, or 29%, or 30%, or 31%, or 32%, or 33%, or 34%, or 35%, or 36%, or 37%, or 38%, or 39%, or 40%, or 41%, or 42%, or 43%, or 44%, or 45%, or 46%, or 47%, or 48%, or 49%, or 50% of the mass of the active ingredient.

[0097] The shape of the defluorinating agent described in the first aspect of the present application is not particularly limited. According to a preferred embodiment, the defluorinating agent is a spherical or cylindrical particle.

[0098] The size of the defluorinating agent described in the first aspect of the present application is not particularly limited. According to a preferred embodiment, the size of the defluorinating agent is 1 to 15 mm, or 2 to 12 mm.

[0099] According to a non-limiting embodiment, the size of the defluorinating agent described in the first aspect of the present application may be 1 mm, or 1.5 mm, or 2 mm, or 2.5 mm, or 3 mm, or 3.5 mm, or 4 mm, or 4.5 mm, or 5 mm, or 5.5 mm, or 6 mm, or 6.5 mm, or 7 mm, or 7.5 mm, or 8 mm, or 8.5 mm, or 9 mm, or 9.5 mm, or 10 mm, or 10.5 mm, or 11 mm, or 11.5 mm, or 12 mm, or 12.5 mm, or 13 mm, or 13.5 mm, or 14 mm, or 14.5 mm, or 15 mm.

[0100] Methods and devices for measuring the size of defluorinating agents are known to those skilled in the art. According to an exemplary embodiment, the size of the defluorinating agent described in the first aspect of the present application is measured by the following method: 32 defluorinating agents are randomly selected, and the size of the defluorinating agents is measured using a digital caliper, and then the average size of the defluorinating agents is obtained. However, it is known to those skilled in the art that other equivalent methods can be used to measure the size of the defluorinating agent.

[0101] The defluorinating agent described in the first aspect of the present application is prepared by a method comprising the following steps:

[0102] 1) mixing components a) to f) to obtain a first mixture;

[0103] 2) forming the first mixture into first particles;

[0104] 3) treating the first particles at a temperature T1 to obtain the defluorinating agent, wherein the temperature T1 ranges from 500 to 700°C.

[0105] Step 1) can be completed by equipment well known to those skilled in the art. As non-limiting examples, high-speed mixers, planetary mixers, single screw extruders, twin screw extruders, internal mixers, and stirrers can be mentioned. However, it should be understood by those skilled in the art that the equipment that can be used to complete the above step 1) is not limited to those mentioned above.

[0106] Step 2) can be performed by equipment known to those skilled in the art. In a preferred embodiment, the above step 2) can be performed in a pill making machine. The pill making machine can be obtained, for example, from Shanghai Tianhe Machinery Equipment Co., Ltd. with the brand ZW-18.

[0107] Those skilled in the art know that when a pelletizing machine is used to complete the above step 2), the rotation speed and gear pitch of the pelletizing machine can be adjusted according to the desired size of the first particles.

[0108] According to one embodiment, the above step 2) is completed at a rotation speed of 5rpm to 500rpm. According to non-limiting embodiments, the rotation speed of the pill making machine can be 5rpm, or 10rpm, or 15rpm, or 20rpm, or 25rpm, or 30rpm, or 35rpm, or 40rpm, or 45rpm, or 50rpm, or 55rpm, or 60rpm, or 65rpm, or 70rpm, or 75rpm, or 80rpm, or 85rpm, or 90rpm, or 95rpm, or 100rpm, or 110rpm, or 120rpm, or 130rpm, or 140rpm, or 150rpm, or 160rpm, or 170rpm, or 180rpm, or 190rpm, or 200rpm, or 210rpm, or 220rpm, or 230rpm, or 240rpm, or 250rpm, or 260rpm, or 270rpm, or 280rpm, or 290rpm, or 300rpm, or 310rpm, or 320rpm, or 330rpm, or 340rpm, or 350rpm, or 360rpm, or 370rpm, or 380rpm, or 390rpm, or 400rpm, or 410rpm, or 420rpm, or 430rpm, or 440rpm, or 450rpm, or 460rpm, or 470rpm, or 480rpm, or 490rpm, or 500rpm.

[0109] According to one embodiment, the gear spacing of the pelletizing machine in step 2) can be 1 to 20 mm, or 3 to 10 mm. According to non-limiting embodiments, the gear spacing of the pelletizing machine in step 2) can be 1 mm, or 2 mm, or 3 mm, or 4 mm, or 5 mm, or 6 mm, or 7 mm, or 8 mm, or 9 mm, or 10 mm, or 11 mm, or 12 mm, or 13 mm, or 14 mm, or 15 mm, or 16 mm, or 17 mm, or 18 mm, or 19 mm, or 20 mm.

[0110] The duration of step 3) can be adjusted according to the desired properties of the defluorinating agent. According to a non-limiting embodiment, step 3 can be performed for 6 to 18 hours.

[0111] According to one embodiment, the defluorinating agent described in the first aspect of the present application may have a porous structure.

[0112] According to one embodiment, the pore diameter of the defluorinating agent is 2 to 50,000 nm, or 5 to 10,000 nm, or 5 to 5,000 nm, or 5 to 2,500 nm, or 5 to 1,000 nm, or 5 to 500 nm.

[0113] According to a non-limiting embodiment, the pore diameter of the defluorinating agent described in the first aspect of the present application may be 2nm, or 3nm, or 4nm, or 5nm, or 6nm, or 7nm, or 8nm, or 9nm, or 10nm, or 11nm, or 12nm, or 13nm, or 14nm, or 15nm, or 16nm, or 17nm, or 18nm, or 19nm, or 20nm, or 50nm, or 100nm, or 200nm, or 500nm, or 1000nm, or 2000nm, or 5000nm, or 10000nm.

[0114] The method for measuring the pore diameter of the defluorinating agent is known to those skilled in the art. In an exemplary and non-limiting embodiment, the pore diameter of the defluorinating agent is measured by a low-temperature N2 adsorption and desorption test. For example, the ASAP 2020-M fully automatic physical adsorption micropore analyzer of Micromeritics, USA, can be used to vacuum degas the sample, and nitrogen is used as the adsorbent to measure the pore size distribution of the sample. The pore size distribution is calculated according to the Barrett-Joyner-Halenda (BJH) model. However, those skilled in the art know that the pore diameter of the defluorinating agent in this application can be measured by other equivalent methods.

[0115] The specific surface area of ​​the defluorinating agent can be measured by the BET method.

[0116] According to one embodiment, the BET specific surface area of ​​the defluorinating agent described in the first aspect of the present application is 2 to 200 m 2 / g, or 2 to 150m 2 / g, or 2 to 100m 2 / g, or 2 to 50m 2 According to a non-limiting embodiment, the BET specific surface area of ​​the defluorinating agent described in the first aspect of the present application is 2m 2 / g, or 5m 2 / g, or 10m 2 / g, or 15m 2 / g, or 20m 2 / g, or 25m 2 / g, or 30m 2 / g, or 35m 2 / g, or 40m 2 / g, or 45m 2 / g, or 50m 2 / g, or 55m 2 / g, or 60m 2 / g, or 65m 2 / g, or 70m 2 / g, or 75m 2 / g, or 80m 2 / g, or 85m 2 / g, or 90m 2 / g, or 95m 2 / g, or 100m 2 / g, or 105m 2 / g, or 110m 2 / g, or 115m 2 / g, or 120m 2 / g, or 125m 2 / g, or 130m 2 / g, or 135m 2 / g, or 140m 2 / g, or 145m 2 / g, or 150m 2 / g, or 155m 2 / g, or 160m 2 / g, or 165m 2 / g, or 170m 2 / g, or 175m 2 / g, or 180m 2 / g, or 185m 2 / g, or 190m 2 / g, or 195m 2 / g, or 200m 2 According to a non-limiting embodiment, the BET specific surface area of ​​the defluorinating agent described in the first aspect of the present application can be 2m 2 / g, or 3m2 / g, or 4m 2 / g, or 5m 2 / g, or 6m 2 / g, or 7m 2 / g, or 8m 2 / g, or 9m 2 / g, or 10m 2 / g, or 11m 2 / g, or 12m 2 / g, or 13m 2 / g, or 14m 2 / g, or 15m 2 / g, or 16m 2 / g, or 17m 2 / g, or 18m 2 / g, or 19m 2 / g, or 20m 2 / g, or 21m 2 / g, or 22m 2 / g, or 23m 2 / g, or 24m 2 / g, or 25m 2 / g, or 26m 2 / g, or 27m 2 / g, or 28m 2 / g, or 29m 2 / g, or 30m 2 / g, or 31m 2 / g, or 32m 2 / g, or 33m 2 / g, or 34m 2 / g, or 35m 2 / g, or 36m 2 / g, or 37m 2 / g, or 38m 2 / g, or 39m 2 / g, or 40m 2 / g.

[0117] The method for measuring the BET specific surface area of ​​the defluorinating agent is known to those skilled in the art. In a non-limiting embodiment, the BET specific surface area of ​​the defluorinating agent is measured by a low-temperature N2 adsorption and desorption test. The ASAP 2020-M fully automatic physical adsorption micropore analyzer of Micromeritics, USA, can be used to vacuum degas the sample, and nitrogen is used as the adsorbent to measure the specific surface area of ​​the sample. The specific surface area is calculated according to the Barrett-Emmett-Teller (BET) method. However, those skilled in the art know that the BET specific surface area of ​​the defluorinating agent in this application can be measured by other equivalent methods.

[0118] The second aspect of the present application relates to a method for preparing a fluorine agent, the method comprising the following steps:

[0119] 1) Mix the following components to obtain a first mixture:

[0120] a) a metal compound comprising a cation of a metal M and a counter cation X

[0121] b) a carrier,

[0122] c) strength agents,

[0123] d) a binder,

[0124] e) extrusion aids,

[0125] f) peptizing agent;

[0126] 2) forming the first mixture into first particles;

[0127] 3) treating the first particles at a temperature T1 to obtain the defluorinating agent, wherein the temperature T1 ranges from 500 to 700°C.

[0128] The components a) to f) and each step in the second aspect of the present application are the same as those described in the first aspect of the present application.

[0129] The third aspect of the present application relates to the use of the defluorinating agent described in the first aspect of the present application or the defluorinating agent prepared by the method described in the second aspect of the present application for removing HF from a HCl / HF mixture as a raw material.

[0130] According to one embodiment, the HF content in the raw material is 10 to 1000 ppm by weight.

[0131] The applicant of the present application unexpectedly discovered that, by combining the specific components as in the first aspect of the present application, the defluorinating agent obtained by a one-pot process can efficiently remove HF from the HCl / HF mixture and has good mechanical properties (including but not limited to compressive strength) and cyclic performance.

[0132] According to one embodiment, the defluorinating agent described in the first aspect of the present application reduces the HF content in the raw material to 0.01 to 2% of the raw material.

[0133] Example

[0134] The present application will now be further described in conjunction with the following examples. However, it should be clear that the following examples are merely illustrative and not restrictive. The scope of protection of the present application is limited only by the attached claims.

[0135] The reagents and equipment used in the examples of this application are as follows:

[0136] Aluminum hydroxide: analytical grade, purchased from Shanghai Titan Technology Co., Ltd.;

[0137] Calcium chloride: analytical grade, purchased from Shanghai Titan Technology Co., Ltd.;

[0138] Magnesium chloride: analytical grade, purchased from Shanghai Titan Technology Co., Ltd.;

[0139] Kaolin: analytical grade, purchased from Shanghai Titan Technology Co., Ltd.;

[0140] Diatomaceous earth: analytical grade, purchased from Shanghai Titan Technology Co., Ltd.;

[0141] Bentonite: analytical grade, purchased from Shanghai Titan Technology Co., Ltd.;

[0142] Montmorillonite: analytical grade, purchased from Shanghai Titan Technology Co., Ltd.;

[0143] Aluminum sulfate: analytical grade, purchased from Shanghai Titan Technology Co., Ltd.;

[0144] Calcium acetate: analytical grade, purchased from Shanghai Titan Technology Co., Ltd.;

[0145] Calcium lactate: analytical grade, purchased from Shanghai Titan Technology Co., Ltd.;

[0146] Calcium carbonate: analytical grade, purchased from Shanghai Titan Technology Co., Ltd.;

[0147] Magnesium carbonate: analytical grade, purchased from Shanghai Titan Technology Co., Ltd.;

[0148] Starch: analytical grade, purchased from Shanghai Titan Technology Co., Ltd.;

[0149] Polyvinyl alcohol: analytical grade, purchased from Shanghai Titan Technology Co., Ltd.;

[0150] Guar gum: analytical grade, purchased from Shanghai Titan Technology Co., Ltd.;

[0151] Sesbania odorata powder: analytical grade, purchased from Shanghai Titan Technology Co., Ltd.;

[0152] Methylcellulose M15: analytical grade, purchased from Shanghai Titan Technology Co., Ltd.;

[0153] Methylcellulose M400: analytical grade, purchased from Shanghai Titan Technology Co., Ltd.;

[0154] Hydroxypropyl cellulose: analytical grade, purchased from Shanghai Titan Technology Co., Ltd.;

[0155] Carboxymethyl cellulose: analytical grade, purchased from Shanghai Titan Technology Co., Ltd.;

[0156] Silica sol: analytical grade, purchased from Shanghai Titan Technology Co., Ltd.;

[0157] Pellet making machine: purchased from Shanghai Tianhe Machinery Equipment Co., Ltd., brand ZW-18;

[0158] Mixer: purchased from Hobart Equipment Co., Ltd., USA, brand N50;

[0159] Particle size: purchased from Shanghai Measuring Tool Factory Co., Ltd., 3V lithium battery digital caliper

[0160] HF concentration at the outlet: Focusing Technology (Hangzhou) Co., Ltd., laser gas analyzer (LGA-4500)

[0161] Compression strength: Dalian Penghui Technology Development Co., Ltd., DLⅢ particle strength tester

[0162] BET specific surface area: Micromeritics, USA, ASAP 2020-M fully automatic physical adsorption micropore analyzer

[0163] Pore ​​diameter: Micromeritics, USA, ASAP 2020-M fully automatic physical adsorption micropore analyzer

[0164] Example 1

[0165] The defluorinating agent is prepared by the following steps:

[0166] (1) weighing 200 g of aluminum hydroxide, 20 g of aluminum sulfate, 60 g of kaolin, 10 g of starch, 10 g of methyl cellulose M15, and 84 ml of silica sol in sequence, placing them in a blender, and stirring them at a constant speed to form a uniform mass, thereby obtaining a first mixture;

[0167] (2) placing the first mixture in a chamber of a pelletizing machine, setting the gear speed of the pelletizing machine to 60 rpm, and setting the gear pitch of the pelletizing machine to 5 mm, to obtain first particles of uniform size;

[0168] (3) The first particles were dried at room temperature overnight, then placed in an oven at 80°C for 6 h, and finally placed in a muffle furnace for calcination at 550°C for 12 h in an air atmosphere at a heating rate of 1°C / min to obtain defluorinating agent microspheres with a uniform pore structure.

[0169] The prepared defluorinating agent microspheres were subjected to a dehydrofluorination test, and the process conditions were as follows:

[0170] The fixed bed reactor tube is filled with defluorinating agent particles. The reactor tube is 60 cm long and 2 cm in diameter. The air velocity of fluorinated hydrogen chloride is 100 h -1 , the hydrogen fluoride concentration was 650ppm, the reaction temperature was 25°C, and the reaction pressure was 1.5 barg. The HF concentration at the outlet was recorded 1h, 500h, 1000h, 1500h and 2000h after the reaction started.

[0171] The above process was used to test the cyclic performance of the prepared defluorinating agent microspheres. Each cycle was carried out for 500 hours, and the HF concentration at the outlet was recorded 1 hour after the start of each cycle and 500 hours later.

[0172] Example 2

[0173] The defluorinating agent is prepared by the following steps:

[0174] (1) weighing 200 g of calcium fluoride, 20 g of calcium acetate, 100 g of diatomaceous earth, 15 g of polyvinyl alcohol, 4 g of hydroxypropyl cellulose, and 64 ml of silica sol in sequence, placing the mixture in a blender, and blending the mixture at a constant speed to obtain a first mixture;

[0175] (2) placing the first mixture in a chamber of a pelletizing machine, setting the gear speed of the pelletizing machine to 120 rpm, and setting the gear pitch of the pelletizing machine to 4 mm, to obtain defluorinating agent microspheres of uniform size, which are referred to as first particles;

[0176] (3) The first particles were dried at room temperature overnight, then placed in an oven at 80°C for 6 h, and finally placed in a muffle furnace for calcination at 550°C for 10 h in an air atmosphere at a heating rate of 1.5°C / min to obtain defluorinating agent microspheres with a uniform pore structure.

[0177] The process conditions for gas phase defluorination are the same as those in Example 1.

[0178] Example 3

[0179] The defluorinating agent is prepared by the following steps:

[0180] (1) weighing 200 g of calcium chloride, 30 g of calcium carbonate, 40 g of bentonite, 4 g of guar gum, 20 g of carboxymethyl cellulose, and 68 ml of silica sol in sequence, placing the mixture in a blender, and blending the mixture at a constant speed to obtain a first mixture;

[0181] (2) placing the first mixture in a chamber of a pelletizing machine, setting the gear speed of the pelletizing machine to 120 rpm, and setting the gear pitch of the pelletizing machine to 3 mm, to obtain defluorinating agent microspheres of uniform size, which are referred to as first particles;

[0182] (3) The first particles were dried at room temperature overnight, then placed in an oven and dried at 80°C for 12 h, and finally placed in a muffle furnace and calcined at 600°C for 12 h in an air atmosphere at a heating rate of 1°C / min to obtain defluorinating agent microspheres with a uniform pore structure.

[0183] The process conditions for gas phase defluorination are the same as those in Example 1.

[0184] Example 4

[0185] The defluorinating agent is prepared by the following steps:

[0186] (1) weighing 200 g of magnesium chloride, 10 g of magnesium carbonate, 80 g of montmorillonite, 5 g of sesbania powder, 8 g of methyl cellulose M400, and 116 ml of silica sol in sequence, placing them in a blender, and stirring them at a constant speed to form a uniform mass, thereby obtaining a first mixture;

[0187] (2) placing the first mixture in a chamber of a pelletizing machine, setting the gear speed of the pelletizing machine to 180 rpm, and setting the gear pitch of the pelletizing machine to 5 mm, to obtain defluorinating agent microspheres of uniform size, which are referred to as first particles;

[0188] (3) The first particles were dried at room temperature overnight, then placed in an oven at 80° C. for 12 h, and finally placed in a muffle furnace for calcination at 650° C. for 12 h in an air atmosphere at a heating rate of 1° C. / min to obtain defluorinating agent microspheres with a uniform pore structure.

[0189] The process conditions for gas phase defluorination are the same as those in Example 1.

[0190] Example 5 : Example 1 was repeated except that no kaolin was used.

[0191] Example 6 Example 1 was repeated except that aluminum sulfate was not used.

[0192] Example 7 Example 1 was repeated except that no starch was used.

[0193] Example 8 Example 1 was repeated except that methylcellulose M15 was not used.

[0194] Example 9 : Example 1 was repeated except that no silica sol was used.

[0195] The amounts of the raw materials used in each embodiment are shown in Table 1 below:

[0196] Table 1 Raw material dosage (g)

[0197]

[0198] The mechanical properties of the defluorinating agent obtained in each embodiment and the HF concentration at the outlet of the reaction device are shown in Table 2:

[0199] Table 2

[0200]

[0201]

[0202] *ND: Not Detected

[0203] The results in Examples 5 to 9 show that if the composition does not contain any of the carrier, strength agent, adhesive, extrusion aid and peptizing agent, the obtained defluorination agent cannot have both good mechanical properties and cycle performance. In particular, after five particle size cycle tests, the HF concentration in the material obtained at the outlet in Examples 5 to 9 is higher than that in Example 1.

[0204] In particular, Example 9 shows that if the defluorinating agent composition does not contain a peptizing agent, the compressive strength of the defluorinating agent is significantly reduced (Example 1: 146.1 MPa; Example 9: 75.4 MPa).

[0205] In particular, the results in Example 7 show that if the defluorinating agent composition does not contain a binder, the HF concentration in the outlet material is significantly higher than that in Example 1 after five cycles (Example 1: 5.5 ppm; Example 7: 9.4 ppm).

[0206] In summary, the results in Tables 1 to 2 show that the defluorinating agent of the present application allows for efficient removal of HF from the HCl / HF mixture, and allows for good mechanical properties (including but not limited to compressive strength) and cycle performance. In the defluorination-deregeneration cycle, the defluorinating agent of the present application always maintains good HF removal performance.

[0207] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A defluorinating agent, wherein the raw materials of the defluorinating agent include: a) an active ingredient, wherein the active ingredient is a metal compound MX, wherein M is a metal, and X is an atom or an atomic group or an ion that forms a compound with M; b) a carrier, c) strength agents, d) a binder, e) extrusion aids, f) a peptizing agent, The defluorinating agent is prepared by the following method comprising the following steps: 1) mixing components a) to f) to obtain a first mixture; 2) forming the first mixture into first particles; 3) treating the first particles at a temperature T1 to obtain the defluorinating agent, wherein the temperature T1 ranges from 500 to 700°C.

2. The defluorinating agent according to claim 1, wherein the defluorinating agent has one or more of the following characteristics: (1) The metal M in the metal compound is selected from one or more of alkali metals, alkaline earth metals, Group III metals, and transition metals. Preferably, the metal M is selected from one or more of Mg, Ca, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Zn; More preferably, the metal M is selected from one or more of Ca, Mg, and Al; (2) The carrier is selected from one or more of aluminosilicates, silicates, silicon dioxide, layered oxides, and carbon materials, Preferably, the carrier is selected from one or more of bentonite, montmorillonite, kaolin, silicon dioxide, diatomaceous earth, and porous carbon materials; (3) The mass of the carrier is 10 to 60% of the mass of the active ingredient; (4) The strength agent is selected from metal carbonates, metal carboxylates, metal sulfates, and any combination thereof, Preferably, the metal in the strength agent is selected from one or more of calcium, magnesium and aluminum; (5) The mass of the strength agent is 1 to 20% of the mass of the active ingredient; (6) The binder is selected from one or more of starch compounds, cellulose compounds, polyvinyl alcohol, sodium alginate, and chitosan, Preferably, The starch compound is selected from one or more of starch, sesbania powder, and guar gum; and / or The cellulose compound is selected from one or more of methyl cellulose, ethyl cellulose, hydroxypropyl cellulose and carboxymethyl cellulose; (7) The mass of the binder is 1 to 10% of the mass of the active ingredient; (8) The peptizing agent is silica sol; (9) The mass of the peptizing agent is 10 to 50% of the mass of the active ingredient; (10) The size of the defluorinating agent is 1 to 15 mm, or 2 to 12 mm; (11) The pore diameter of the defluorinating agent is 2.5 to 50000 nm; (12) The BET specific surface area of ​​the defluorinating agent is 2 to 200 m 2 / g.

3. The defluorinating agent according to claim 1, wherein the defluorinating agent has at least one of the following characteristics: (1) Step 2) is carried out in a pelletizing machine; (2) Step 2) is performed at a rotation speed of 5 rpm to 500 rpm; (3) Step 2) is performed at a gear pitch of 1 to 20 mm; (4) The first particles obtained in step 2) are spherical or cylindrical particles; (5) The step 3) is performed for 6 to 18 hours.

4. A method for preparing a defluorinating agent, the method comprising the following steps: 1) Mix the following components to obtain a first mixture: a) an active ingredient, wherein the active ingredient is a metal compound MX, wherein M is a metal, and X is an atom or an atomic group or an ion that forms a compound with M, b) a carrier, c) strength agents, d) a binder, e) extrusion aids, f) peptizing agent; 2) forming the first mixture into first particles; 3) treating the first particles at a temperature T1 to obtain the defluorinating agent, wherein the temperature T1 ranges from 500 to 700°C.

5. The method of claim 4, wherein the method has at least one of the following features: (1) Step 2) is carried out in a pelletizing machine; (2) Step 2) is performed at a rotation speed of 5 rpm to 500 rpm; (3) Step 2) is performed at a gear pitch of 1 to 20 mm; (4) The step 3) is performed for 6 to 18 hours.

6. Use of the defluorinating agent according to any one of claims 1 to 3 for removing HF from a HCl / HF mixture as a raw material, Preferably: The HCl / HF mixture has a HF content of 10 to 1000 ppm by weight; and / or The defluorinating agent reduces the HF content to 0.01 to 2% in the raw material.

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